Method of hydrocarbon oil conversion



' Feb. 24, 1942. B. sHr-:PPARD 25274903 METHOD OF HYDROCARBON OIL CONVERSION lFiled July 6, 1939 Seac-E .5A/5,010,420

i BY AT'rbRNEY Patented Feb. 24, 1942 ICE METHOD oF HYDROCARBON oir.

CONVERSION Bruce Sheppard, Bridgewater Township, Somerset County, N. J., assignor to Petroleum Conversion Corporation, Elizabeth, N. J., a corporation of Delaware Application July 6, 1939, Serial No. 232,980

(Cl. s-.52

1 Claim.

My present invention relates to improvements in the art of hydrocarbon oil conversion, particularly in methods involving conversion in the presence of a solid contact agent, whichmay act by adsorption, orcatalysis, or decarbonization or otherwise. i

It is a principal object of my invention to provide an improved method in which the hydrocarbon material to be converted is passed continuously through a moving column of the convtact agent. In certain respects my present ,in-

vention may be regarded as an improvement over that disclosed and claimed-in my co-pending application Serial No.'279,282 led June l5, 1939; but whereas the method of said pending application is essentially a' batch onel the present invention provides for a method which is completely continuous. Incarrying out my improved method, fresh contact material extraneous to the conversion system proper is admitted and the spent material Withdrawn substantially continuously from the reaction chamber which is maintained under superatmospheric pressure.

Other objects of the invention and advantages thereof will be apparent as the description proceeds.

The invention will be best understood by reference to the following detailed description taken with the annexed drawing, in which the single ligure shows a suitable apparatus for carrying out a preferred embodiment of my invention.

Hopper I, which may be open to the atmosphere or closed loosely by hinged cover 2, in which case' an outlet pipe 3 leading to a stack (not shown) is provided, Contains the fresh contact agent 4 supplied to it from time to time or continuously, by means not shown. Heated gaseous iiuid of suitable type, as for example flue gas, obtained from any convenient source, is passed through the hopper I by pipe 5 and serves to displace the air and to preheat the contact agent to the desiredinitial temperature, which may be, for example, 450 F. more or less; it being one of the advantages of the present system that the preheating of the solid contactagent does not introduce gases in appreciable quantity into the reaction zone with the necessity for subsequent treatmentof the additional gas volumes. The contact material 4 is fed from the hopper I in measured amounts by action of a measuring valve 6 which may be of the star type, the same being actuated by mechanism which includes a ratchet Wheel 1, pawl 8 and lever 9. Material moved from the chamber I by the valve 6 is deposited in an upper chamber Il! upon a slide valve II.

Slide or sealing valve II opens into pressuring chamber I2 therebeneath, but only at such times that said chamber has been depressured substantially to atmospheric pressure. When sealing valve II has allowed the measured quantity of Contact agent in chamber I 0 to drop into chamber I2, sealing valve II is closed without having to out through any solid material and locks oi chamber I2 completely from chamber IIJ. When chamber I2 receives its charge through the open sealing valve II a further sealing valve I3, forming when closed the floor of chamber I2, is completely closed, cutting off the chamber I2 from the reaction chamber I4. When the measured charge of contact agent from the upper chamber ID is dropped through open sealing valve II into chamber I2, sealing 'Valve I I'again locks, Vor is locked, and pressure in the chamberl I2 is increased to equal or slightly exceed the pressure in chamber I4 by admitting heated gas under suitable pressure through line I5 preferably by means of an automatically controlled 'valvey I6, operated by mechanism not shown. When cham ber I2 has been suitably pressured, 'the line I5 is Vlocked 01T, sealing valve I3 opens, vand the measured charge of contact material drops through openv sealing valve I3 into pipe I1 which extends down into reaction; chamber I4. Chamber I2, after 'it has allowed itsimeasured charge to drop through sealing valve I3, is cut off from the conversion system by closing valve I3, and is depressured by means of line I5 by the opening of the valve I 6 therein.

At the lower end of reaction chamber I4 is a discharge system corresponding to the feed system at the upper end. Here measuring valve 2D corresponds to valve 6. The amount of contact material measured off by each segment of the valve 20 drops into chamber 2| above slide valve 22 above sealing valve 23, said valves dening a pressure chamber 25. Pressure chamber 25 having been brought to a pressure equal to that prevailing in the reaction chamber I4 by means of gas under suitablel pressure admitted through line 26 controlled by valve 21 automatically regulated by means-not shown, the sealing valve 22 opens, a measured amount of spent contact agent in chamber 2| drops into chamber 25, the sealing valve 23 thereupon being closed. Chamber 25 is then depressured by means of line 26 until the pressure is substantially atmospheric. The released gas from the line 26 may be recovered by suitable means for re-use within the process. When chamber 25 has been depressured, sealing valve 23 opens, or is opened, and permits the measured charge of spent contact material to drop into line 28 connected with a receiving vessel (not shown). may be a stationary vessel from which the spent contact agent is removed periodically or continuously to a system of 'regeneration for said material, or it may be a removable vessel or car which is moved periodically with its contents and replaced by an empty vessel or car. Regeneration of the spent contact material is vcarried out by any suitable means and the regenerated contact agent to which is added from time to time The receiver below valve 23 l make-up material to compensate for the ,amount lost by dusting, etc., is returned periodically or continuously as by an endless belt system (not shown) to hopper I. Valves E, II, I3, 20, 22,23, I6 and 21, shown, may be manually operated, but preferably said valves are operated by automatically controlled means (not completely shown on the drawing), such means providing for the desired timing of the motions. n

In operation, after the reaction chamber has been lled with contact material to the level shown, oil vapor brought to a temperature of, for example, 850y more or less, by means not shown, is admitted to column I4 and into the body of the contact substance by one or more pipes, as for example, pipes 30, 3|, shown, and after passing through the contact mass, exits from the column by pipes 32, 33 which lead to a recovery system, not shown.'v Pipe 35, disposed preferably below measuring valve 20, admits a regulated quantity /of gas, which may be a hydrocarbon gas or other gas; substantially inert in the above process, at a temperature lower than that of the column of contact material in chamber I4. The function of this gas is to cool that part of ther contact mass extending below pipes 30 and 3| while the gas itself becomes heated, and to assist in vsweeping the vapors through the column of contact material to dry the lower part of the contact column so as to render the contact substance, which may be in the form of lumps, pellets or granules, more freely flowing. In order to prevent loss of heat by radiation and conduction from column I4, it may be surrounded or insulated by heat insulating material 36 between which and the walls of the chamber I4 is a jacket 31 receiving heated fluid, as for instance, flue gas, by pipe 39, the heating fluid leaving the jacket through pipe 40, theheated fluid being at such a temperature, say 860870 F., as to prevent a Adrop in temperature of the vapors and gases passing through the contact mass.

The course of a given portion of contact agent through the apparatus is as follows: It is dropped into hopper I, moves slowly downwardly against a current of heated flue gas and becomes heated in the hopper to about 450 F. It is picked up by measuring valve B, dropped into chamber I0, and finally falls through sealing valve II into chamber I2 where it Vis subjected to gas pressure equal to that existing in the chamber I4. It then falls through sealing valve I3 into pipe I1 and descends as part of the column in the reaction chamber I4, gradually reaching a temperature, say, of 850 F. It passes down through the reaction chamber I4 countercurrently to a rising stream of vapor to be converted and becomes coated and spent. As it descends below pipes 3D and 3| it is somewhat cooled, is measured out of the chamber I4 by'valve 20, is dropped into chamber 2| and then falls through sealing valve 22 into chamber 25 where it is relieved of pressure and falls through sealing valve 23 and thence into a receiver, not shown, after which it is regenerated and passed, by means not shown, into hopper I. The motions of the several valves shown, already mentioned as automatically operated, are preferably all controlled from one master point and synchronized so that the rate of entry of the contact substance in the system equals the exit rate of contact substance v from the system, in such manner maintaining the desired superatmospheric \pre'ssure in thechamber Valves II, I3. 22 and 23 are of the to the use of these contact substances.

v pressure obtaining in the reaction chamber may quick acting gate type with self-cleaning faces so that the passage from the fully closed to the fully open position is rapid. The amount #measured out by the measuring valves 6 and 20 for each valve cycle is less than the capacity of the pressure chambers I2 and 25, so that said valves I I, I3, 22 and 23 do not at any time close against the body of solid contact substance.

If it is desiredto add gas to the reaction zone either to supply additional heat or to provide for sweeping the gas toward the exit lines 32 and 33, one or more inlets for such gas may be provided, of which only one is shown by way of example as line 42.

As contact agents to be used in the present method I have found suitable silica gel in granular form, either as such ,or withv certain substances -deposited thereon such as aluminum oxide obtained by treatment with aluminum acetate solution followed by heating to 850 F., more or less, or granular Filtrol or various forms of activated carbons, but my invention is not limited The be any suitable value, as for example, from 10 pounds to 2,00 pounds per square inch gage.

In lieu of the measuring valves 6 and 20, valves of other types may be provided, as for example, that shown in Figures 2 and 6 of my co-pending application Serial No. 279,282 led June 15, 1939, the same being the invention of William E. Joor, Jr., described and claimed in his co-pending application Serial No. 287,891 filed August 2, 1939.

While lI have illustrated and described in detail certain preferred forms of my invention, it is to be understood that changes may be made therein and the invention embodied in other structures. I do not, therefore, desire to limit myself to the specific construction illustrated, but intend to cover my invention broadly in whatever form its principle may be utilized.

In a continuous method of hydrocarbon oil conversion in which the conversion is brought about in the vapor phase in the presence of and by the action of a solid contact material or agent in divided form disposed in a reaction chamber maintained under superatmospheric pressure, the

improvement which consists in establishing a' downwardly moving column of said divided contact material in said reaction chamber by feeding successive measured quantities ofsaid material into a material receiving chamber exterior of but communicating with said reaction chamber, following which event said material receiving chamber is closed against further supply of material and said latter chamber pressured with gas to substantially reaction chamber pressure, after which communication is established between said material receiving chamber and said reaction chamber, thereby allowing said measured quantity of said material to enter the reaction chamber, closing said communication last mentioned, depressuring said material receiving chamber and opening same to the feed of fresh material, continuing the feed of material as aforesaid, passing hydrocarbon vapor to be converted upwardly through the material in said re-I 

